Certain phosphorus-containing imino oxazolidines,thiazolidines and perhydrooxazines

ABSTRACT

WHEREIN X AND Y ARE INDEPENDENTLY OXYGEN OR SULFUR, R1 IS LOWER ALKYL, LOWER ALKOXY, LOWER ALKTHIO; R2 IS LOWER ALKYL, LOWER ALKOXY, LOWER ALKYLTHIO, CHLORO LOWER ALKYL, CARBETHOXY METHYLTHIO, ALLYLTHIO, CHLOROPHENYLTHIO, NITROBENZYLOXY, PHENYL OR SUBSTITUTED PHENOXY IN WHICH SAID SUBSTITUENTS ARE NITRO, CYANO, MMETHYLTHIO, CHLORO OR TERT.-BUTYL; R2 IS LOWER ALKYL, BENZYL, PHENYL, LOWER ALKOXYALKYL, ALLKENYL, CHLOROALKENYL OR 2-PROPYNYL; IN WHICH R4 IS HYDROGEN, LOWER ALKYL, CYCLOHEXYL OR VINYL, R5, R6 AND R7 ARE INDEPENDENTLY HYDROGEN OR LOWER ALKYL; PROVIDED THAT WHEN Q IS -CH2CH2CH2- THEN R3 IS OTHER THAN BENZYL. THE ABOVE-MENTIONED COMPOUNDS ARE BIOLOGICALLY EFFECTIVE AS PESTICIDES, ESPECIALLY AGAINST INSECTS AND ACARIDS, AND AS HERBICIDES. REPRESENTATIVE COMPOUNDS ARE: 2-(N-O,O-DIMETHYLPHOSPHONOTHIONO)-AMINO)-3-ETHYL5-METHYL-1,3-OXAZOLIIDINE 2-(N-O,O-DIETHYLPHOSPHONOTHIONO)-IMINO)-3-ETHYL5-METHYL-1,3-OXAZOLIDINE, 2-(N-(O,S-DIMETHYLPHOSPHONOTHIOLO)-IMINO)-3-ETHYL5-METHYL-1,3-OXAZOLIDINE, 2-(DIETHYLTHIOPOSPHINOIMINO)-3-METHYL OXAZOLIDINE, 2-(O,O-DIMETHYLTHIOPHOSPHORYLIMINO)-3-METHYL THIAZOLIDINE, AND 2-(O,O-DIMETHYLTHIOPHOSPHORYL-IMINO)-3-ALLYL-PERHYDRO-1,3-OXAZINE.   Q IS -C(-R4)(-R5)-C(-R6)(-R7)- OR -(CH2)3-     R1-P(=X)(-R2)-N=C&lt;(-Y-Q-N(-R3)-)   NEW COMPOUNDS CORRESPONDING TO THE FORMULA

3,812,117 CERTAIN PHOSPHORUS-CONTAINING IMINO OXAZOLIDINES,THIAZOLIDINES AND PER- HYDROOXAZINES Edmund J. Gaughan, Kensington,Calif., assignor to Stautfer Chemical Company, New York, N.

No Drawing. Application Mar. 23, 1970, Ser. No. 22,039,

now Patent No. 3,714,176, which is a continuation-inpart of applicationSer. No. 705,017, Feb. 13, 1968, which in turn is a continuation-in-partof application Ser. No. 673,993, Oct. 9, 1967, both now abandoned.Divided and this application Oct. 26, 1972, Ser. No.

Int. Cl. C0711 93/10 US. Cl. 260-243 R 3 Claims ABSTRACT OF THEDISCLOSURE New compounds corresponding to the formula wherein X and Yare independently oxygen or sulfur, R is lower alkyl, lower alkoxy,lower alkylthio; R is lower alkyl, lower alkoxy, lower alkylthio, chlorolower alkyl, carbethoxy methylthio, allylthio, chlorophenylthio,nitrobenzyloxy, phenyl or substituted phenoxy in which said substituentsare nitro, cyano, methylthio, chloro or tert.-butyl; R is lower alkyl,benzyl, phenyl, lower alkoxyalkyl, alkenyl, chloroalkenyl or 2-propynyl;

in which R, is hydrogen, lower alkyl, cyclohexyl or vinyl, R R and R areindependently hydrogen or lower alkyl; provided that when Q is -CH CH CHthen R is other than benzyl.

The above-mentioned compounds are biologically effective as pesticides,especially against insects and acarids, and as herbicides.Representative compounds are:

2-[N-(0,0-dimethylphosphonothiono)-amino] -3-ethyl-5-methyl-l,3-oxazolidine,

2- [N- 0,0-diethylphosphonothiono) -imino] -3-ethyl-5-methyl-1,3-oxazolidine,

2- [N- (0,S-dimethylphosphonothiolo) -imino] -3 -ethyl-5-methyl-1,3-oxazolidine,

2-(diethylthiophosphinoimino)-3-methyl oxazolidine,

2-(0,0-dimethylthiophosphorylirnino) -3 methyl thiazolidine, and

2- (0,0-dirnethylthiophosphoryl-imino) -3-a1lyl-perhydro-1,3-oxazine.

This is a division of application Ser. No. 22,039, filed Mar. 23, 1970,now US. Pat. No. 3,714,176, and a continuation-impart of US. applicationSer. No. 705,017, filed Feb. 13, 1968, now abandoned, which in turn is acontinuation-in-part of US. application Ser. No. 673,993, filed Oct. 9,1967, now abandoned.

The present invention is concerned with a novel group of phosphoryl,thionophosphoryl, phosphonyl, thionophosphonyl, phosphinyl andthionophosphinyl imino oxazolidines, thiazolidines and perhydrooxazines,their method of preparation, and their use as pesticides especiallyeffective against insects, acarids and as herbicides.

United States Patent 9 "ice The novel compounds are represented by thegeneral formula wherein X and Y are independently oxygen or sulfur; R islower alkyl, lower alkoxy, lower alkylthio; R is lower alkyl, loweralkoxy, lower alkylthio, chloro lower alkyl, carbethoxy-methylthio,allylthio, chlorophenylthio, nitrobenzyloxy, phenyl or substitutedphenoxy in which said substituents are nitro, cyano, methylthio, chloroor tert.-butyl; R is lower alkyl, benzyl, phenyl, lower alkoxyalkyl,alkenyl, chloroalkenyl or 2-propynyl;

R5 Rs 1 Q is -('J or -CH2CHqCH:-

I I in which R, is hydrogen, lower alkyl, cyclohexyl or vinyl, R R and Rare independently hydrogen or lower alkyl. Provided that when Q is --CHCH CH then R is other than benzyl.

The lower alkyl radicals which are suitable for R R R R R R and R arethe straight and branched chain aliphatic radicals having from 1 to 6carbon atoms and include, for example, methyl, ethyl, propyl, isopropyl,hexyl and the like. The lower alkoxy radicals for R and R contain from 1to 6 carbon atoms; the lower alkylthio radical for R contains from 1 to6 carbon atoms; and the alkyl in chloro lower alkyl for R contains from1 to 3 carbon atoms. In the lower alkoxyalkyl radical for R the alkoxyand alkyl portions thereof contain from 1 to 3 carbon atoms, forexample, methoxyethyl, ethoxymethyl, ethoxyethyl, propoxypropyl and thelike.

As a consequence of the special geometry of the compounds of thisinvention, the ring structure and restricted rotation within thisstructure, the possibility exists for geometric isomerism. Cir-transisomerism is very frequently encountered in substituted ring structuresof this type. It is recognized that the trans isomers are usually morestable than the corresponding cis isomers. Both stereoisomeric forms arebelieved to exist for the majority of the compounds described hereinwhen possible. The compounds of the present invention are not limited toany specific geometric isomer configuration. In several instances, asseen below, both stereo isomers have been isolated and characterized.The physical properties of czs and tran isomers are usually quitesimilar and separation of both from a mixture by techniques such asfractional distillation or crystallization is not always possible. Atthe same time many of the compounds, due to the several possibleasymmetric centers present in the molecule, have the possibility foroptical stereoisomerism as well as the geometric isomerism, discussedabove. This phenomenon is understood and recognized by those skilled inthe art. The designations D and *L found in Table 1 are used herein toindicate the configuration of the optically pure amino acids from whichthe compounds were made. No reference to the absolute or relativeconfigurations of the final product is expressed or implied. To thoseskilled in the art, it is reasonable that such optical stereoisomerismduced is then reacted with the appropriate beta-hydroxy amine to give athio urea which in the presence of mercuric oxide undergoes cyclizationwith the loss of the elements of hydrogen sulfide and yields the desiredphosphoryl, thiophosphoryl, phosphonyl, thiophosphonyl, phosphinyl orthiophosphinyl imino oxazolidine. The desired product is isolated bythin layer chromatography using methods well known to those skilled inthe art.

The necessary starting imino oxazolidines of the instant invention canbe prepared by the general method which begins with the reaction betweenan epoxide and an appropriate primary amine to give the correspondingamino alcohol. The resulting amino alcohol is then allowed to react withcyanogen bromide in the presence of a caustic such as sodium hydroxideto yield the corresponding 2-imino-1,3-oxazolidine. The oxazolidine isthen phosphorylated with an appropriate phosphoryl halide in thepresence of sodium hydroxide. When a substituted phosphorothionohalidate is used as the phosphorylating agent, the product obtained is aphosphorothiono imino- 1,3-oxazolidine. The resulting thiono compoundcan be rearranged to the thiolo isomer by reaction with an alkyl iodide.The resulting compound is then 2-[O,S(di-substitutedphosphorothiolo)imino] -1,3-oxazolidine.

The preparation of phosphorodithio imino oxazolidines is readilyaccomplished by reacting the appropriate imino oxazolidine with aphosphorothiodichloridate to give a 2-[N(chloro-O-substituted-phosphorothiono)imino] oxazolidine. Thisintermediate is then reacted with a thiol-containing compound in thepresence of caustic to yield the desired 2-[N- (O,S-di-substitutedphosphorodithio)imino] 1,3-oxazolidine.

The thiazolidines of the instant invention also are prepared accordingto the following general description of the synthetic procedure.Compounds of the form C=NHz-halide The free imino base is obtained afterdissolving the imino salt (2) in water and adding one equivalent, ormore, of strong base (e.g. sodium hydroxide solution).

Either the imino salt (2) with two molar equivalents of base as acidacceptor or the free imine base (3) in molar excess or with one molarequivalent of another base is phosphorylated using an alkoxychlorothionophosphate (-phosphonate) in an inert solvent. This reactionis exothermic and the reaction temperature is held below 45 C. bycooling. Bases which can be used as acid acceptors are sodium hydroxide,potassium carbonate, potassium hydrogen carbonate or tertiary aminessuch as triethylamine. Suitable solvents are acetone, methylenechloride, benzene C=NH or heterogeneous mixtures such as benzene/water.The final product isolated has the general structure i. wherein R islower alkyl.

The thionophosphor (-phosphon) amides (4) are rearranged tothiolophosphor- (thiolophosphon-) amides (5 by dissolving them in aninert solvent (erg. benzene, benzene/hexane) and refluxing with alkyliodide (e.g. methyl iodide, ethyl iodide), or by refluxing them directlyin the alkyl iodide. The products are purified by evaporating thesolvent and alkyl iodide reagent, redissolving the crude product in anon-polar solvent such as benzene to precipitate the polar, solidby-product usually accompanying the rearrangement. The benzene solutionis filtered and the solvent removed to give the final product which canbe further purified by recrystallization or chromatography. The productshave the general thiolo structure (5).

wherein R is lower alkyl.

The preparation of the 1,3-perhydrooxazines is carried out by reactingan appropriate substituted amine with ethyl acrylate to produce alit-amino ester. The B-amino ester is reduced with lithium aluminumhydride to the 3-substituted-amino alkanol. The amino alkanol is reactedwith cyanogen bromide (BrCN) in the presence of a base, such as powderedsodium hydroxide to yield the corresponding cyanamide. Treatment of thep-hydroxyalkyl cyanamide with a further quantity of sodium hydroxidepromotes ring-closure to the corresponding imino perhydrooxazine. Theimino perhydrooxazine is phosphorylated with the appropriate phosphoruscontaining acid chloride in a solution, such as benzene, in the presenceof an acid acceptor such as sodium hydroxide. When a thiono phosphoruscompound is prepared, rearrangement of the thiono to thethiolophosphorus compound is accomplished by reaction with an alkyliodide in an appropriate solvent, such as benzene-hexane solution.

The following specific examples are illustrative of general methodsdiscussed herein above.

Preparation of 2-[N- (0,0-diethylphosphonothiono)-imino]-3-ethyl-5-methyl-1,3-oxazolidine To a solution of 38.8 grams (0.4mole) of potassium thiocyanate in 395 ml. of acetone containing 6 gramsof pyridine is added 75.4 grams (0.4 mole) of diethylchlorothiophosphate over a 2 hour period. The mixture is stirred anotherhour at room temperature, then at 45-50" C. for forty-five minutes. Itis filtered from the precipitate of potassium chloride and the solventremoved in vacuo. The residue is taken up in benzene and the insolublematerial removed. The benzene is removed in vacuo and the productdistilled twice, the second time through a Vigreux column. 5.3 grams(0.025 mole) of this product is dissolved in 42 ml. of benzene; 2.7 g.(0.025 mole) of ethyl B-hydroxypropylamine in ml. of benzene is addedover minutes. After letting the mixture stand overnight, the solvent isremoved in vacuo leaving a crystalline product. To a solution of 3.3grams (0.011 mole) of the above product in 50 ml. of benzene is added3.7 grams (0.0167 mole) of mercuric oxide. The mixture is stirred andrefluxed for 3.5 hours. The mixture is filtered and the filtrate driedover magnesium sulfate. The benzene is removed in vacuo leaving a crudeviscous product. This product is taken up in 35 ml. of benzene andrefluxed with 2.0 grams of mercuric oxide for another five hours. Themixture is again filtered, driedand the solvent removed. Pure2-[N-(0,0-diethyl-phosphonothiono) imino]-3-ethyl-5-methyl-1,3-oxazolidine is isolated from the crude product by thin layerchromatography, using solvent systems 90: 10 chloroformzacetone v./v. onsilica gel. Instrumental analysis establishes the above structure andelemental analysis shows 43.18% C, 7.53% H, 9.82% N, 11.23% P, and11.27% S as compared with theoretical values of 43.20% C, 7.55% H,10.00% N, 11.10% P and 11.40% S.

Another general method for the preparation of the O,S phosphoryliminooxazolidines of the present invention consists of reacting the productresulting from the reaction of the appropriate 0,0-phosphorodithioicacid and cyanogen bromide in the presence of triethylamine with theappropriate beta-hydroxyamine and isolating the desired product by thinlayer chromatography using methods well known to those skilled in theart. The following example is illustrative of the above general method.

EXAMPLE 2 CHr-O 2115 CHa-S Preparation of2-[N-(O,S-dimethylphosphonothiolo)-imino]-3-ethyl-5-methyl-1,3-oxazolidine To a solution of 79.0 grams (0.5mole) of 0,0-dimethylphosphonodithiocic acid in 100 ml. of benzene isadded 50.5 grams (0.5 mole) of triethylamine at 15 to 25 C. A solutionof 53 grams (0.5 mole) of cyanogen bromide in 75 ml. of benzene is thenadded over 1.5 hours at 15 C. The reaction mixture is then stirred twomore hours at room temperature, during which time the precipitate ofamine hydrobromide becomes thicker. The mixture is filtered and thebenzene removed from the filtrate in vacuo. The product is distilled at55-58 C./ .751.0 mm. yielding 44.0 grams. 5.5 grams of this intermediateproduct is dissolved in 44 ml. of dry acetone and to the solution isadded a solution of 3.1 grams of ethyl fl-hydroxypropylamine in 15 ml.of acetone. The mixture warms to 32 during addition and is stirred for1.5 hours. The acetone is removed in vacuo and the residue pumped out at0.4 mm. for 1.5 hours, yielding 8 grams. Upon standing, the productpartially crystallizes. After the crystals are removed, the mixture isplaced in 30 ml. of water and the mixture is extracted twice with 80 ml.portions of chloroform. The extract is dried over magnesium sulfate,filtered, and the solvent removed in vacuo. The residual oil is pumpedout at 1 mm. up to 55 C. It is then seeded with one of thesponstaneously formed crystals removed above and allowed to stand untilall of the second component has crystallized out. The mixture It is thenseeded with one of the spontaneously formed chromatography using :10chloroformzacetone v./v.

and :5 ethanolzwater v./v. solvent systems on silica gel, giving pure 2[N-(O,S-dimethylphosphonothiolo)- imino] 3ethyI-S-methyl-1,3-oxazolidine. Instrumental analysis establishes theabove structure and elementalv 6 analysis shows 12.30% P compared to12.30% P theoretical.

Another general method for the preparation of the O,S-phosphoryl iminooxazolidines of the present invention consists of reacting theappropriate 0,0-thiophosphonylimino oxazolidine with the appropriatealkyl or alkenyl iodide to form the desired product, which is isolatedby thin layer chromatography using methods well known to those skilledin the art. The following example is illustrative of the above generalmethod.

Preparation of 2-[N-(-O,S-dimethylphosphorothiolo)- imino]-3-ethyl-5-methyl-1,3-oxazolidine A solution of 7.6 g. (0.03 mole) of2-[N-(0,0-dimethylphosphonothiono)-imino]-3-ethyl 5 methyl 1,3oxazolidine and 4.4 g. (0.031 mole) of methyl iodide in a mixture of .25ml. of hexane and 5 ml. of benzene is refluxed for 5 hours. The mixtureis cooled and filtered and the solvent removed in vacuo.

EXAMPLE 4 Preparation of diethylthiophosphinoisothiocyanatothioatePotassium thiocyanate (65.6 g., 0.75 mole) and a trace of potassiumiodide are place in 500 ml. of dry acetone and warmed to 45.Diethylthiophosphinochloridothioate (78.3 g., 0.5 mole) is addeddropwise at 45-50. A precipitate of potassium chloride appeared. Themixture is then refluxed for 15 minutes. It is cooled, filtered, and thesolvent removed in vacuo. The residue is treated with water and the oilextracted with hexane. The extract is washed with sodium bicarbonatesolution and with water, dried, and the solvent removed in vacuo. Theresidue is distilled twice in vacuo. The product has a boiling point of7980/.3 mm. Yield: 49.0 g. (55% of theory). Its IR spectrum showed aband characteristic of the isothiocyanate group at 2000-2050 cmrPreparation of N-diethylthiophosphinyl-N'-methyl- N'-hydroxyethylthiourea The above-mentioned thioate (26.9 g., .15 mole) is dissolved in75 ml. of benzene and a solution of N-methylethanolamine (12.0 g., .16mole) added dropwise. The temperature increased to 33 during theaddition. Stirring is continued 1 hour at room temperature, 1 hour at65- 70. The reaction mixture is filtered through Celite and evaporatedin vacuo. Upon trituation with hexane, the residue solidified. It isrecrystallized from benzene-hexane, and has a M.P. 68-73. Yield: 23.4 g.(61% of theory).

Preparation of 2-diethylthiophosphinoimino)- 3-methyl oxazolidine Theabove-mentioned thiourea (15.6 g., 0.07 mole) dissolved in ml. ofbenzene is stirred and refluxed with mercuric oxide (32.6 g., 0.15 mole)under a Dean-Stark trap until no more water is given ofi (about 3hours). Black mercuric sulfide appears. The mixture is cooled, filtered,and the filtrate dried over magnesium sulfate. Removal of the solventleft a yellow oil. n =1.5563. Yield: 7.8 g. (51% of theory).

EXAMPLE 5 Preparation of the intermediate 2-imino-3-ethyl-5-methyl-l,3-oxazolidine Ethylaminoisopropanol (20.6 g., .2 mole) isdissolved in 90 ml. of benzene and powdered sodium hydroxide (8.0 g., .2mole) added. This mixture is stirred and a solution of cyanogen bromide(21.2 g., .2 mole) in 50 ml. of benzene added at -15 C. A precipitate ofsodium bromide appeared. The mixture is stirred two hours at roomtemperature, filtered and the solvent removed in vacuo. The residue isdistilled through a Vigreux column B.P. 5759/2 mm. There is obtained ayield of 17.7 g. (69.1%) of the title compound. The IR spectrum showedthe expected bands.

Preparation of 2-(0,0-dimethylthionophosphorylimino)-3-ethyl-5-methyl-1,3-oxazolidine Dimethyl chlorothiophosphate (16.1 g.,.1 mole) is added dropwise at 2025 to a well stirred mixture of theiminooxazolidine (13.4 g., .105 mole) and sodium hydroxidc (4.2 g., .105mole) in 100 ml. of benzene and 25 ml. of water. The mixture is stirredanother four hours, the layers separated, and the organic layer iswashed and dried. Removal of the solvent left a crystalline residuewhich is recrystallized from ether. M.P. 68-71". There is obtained ayield of 18.0 g. (71.4%) of the title compound. The IR spectrum showedthe expected bands. The structure was also confirmed by its NMRspectrum.

Preparation of 2-(O,S-dimethylthiolophosphorylimino)-3-ethyl-5-methyl-1,3-oxazolidine The thiono compound (200 g., .79 mole)and methyl iodide (124.1 g., .87 mole) are refluxed in a mixture of 396ml. of benzene and 598 ml. of hexane for three hours. The solvent isremoved in vacuo and about one liter of dry benzene is added to theresidue. The mixture is allowed to stand over night and filtered throughdiatomaceous earth filter-aid. The benzene is removed in vacuo and theresidue, a viscous yellow oil, pumped out under high vacuum. There isobtained a yield of 188.4 g. (94.2%). IR and NMR spectra confirmed theassigned structure. The product was about 80% pure by quantitativeT.L.C. A chromatographically pure sample isolated by preparative TLC.showed nu 1.5172.

EXAMPLE 6 Preparation of the intermediate: 2-imino-3-methylthiazolidinehydrogen iodide N (III-I3 In a l-liter round bottom flask containing amagnetic stirring bar is dissolved 110 g. (1.08 moles) 2-amino-2-thiazoline in 230 ml. absolute methanol. To this solution are then added153 g. 1.08 moles) methyl iodide. The temperature of the exothermicreaction was held below the boiling point by immersing the flask in acold water bath. Stirring at room temperature is continued overapproximately a 70 hour period. Within this period, a copious amount ofsolid precipitates. The reaction mixture is cooled in the refrigeratorand the solid filtered. Concentration of the filtrate gives anadditional crop of product. After drying, a total of 220.9 g. of crudeproduct is isolated, M.P. 149159 C. Recrystallization of this materialgives 207.6 g. of long, colorless needles, M.P. 160.5-162 C. Yield: 79%of theory. (Literature, M.P. 159-460, S. Gabriel, Ben, 22, 1146 (1889).)

The free imine is obtained by mixing 66.9 g. (0.274 moles)2-imino-3-methylthiazolidine hydrogen iodide with 30 ml. water andadding, with cooling in an ice bath, 40 ml. of 25% (w./w.) sodiumhydroxide solution. .A pH of about 10 is reached. The resulting solutionis extracted continuously with benzene for two days using a liquidliquidextraction apparatus. The benzene solution is dried over anhydrousmagnesium sulfate, filtered and the benzene is evaporated. The residueis distilled through a 10 cm. Vigreaux column. There is collected 21.2g. of product, B.P. 96-965 C./ 4.1 torr. Yield: 67% of theory.(Literature: B.P. 119120 C./20 torr., K. K. Kuzmina et al., Zh. Obsch.Khim., 32, 3215 (1962).]

EXAMPLE 7 2-(0.0-dimethylthiophosphorylimino)- 3-methylthiazolidine Intoa 500 ml. four-neck round bottom flask provided with a stirred,thermometer and pressure equalizing funnel are placed 16.9 g. (0.0694moles) 2-imino-3-methylthiazolidine hydrogen iodide, 100 ml. benzene and22.2 g. (0.139 equivalents) of 25% (w./w) sodium hydroxide solution.This heterogeneous mixture is stirred vigorously as 11.2 g. (0.0694moles) 0,0-dimethyl chlorothiophosphate dissolved in 30 ml. of benzeneare addeddropwise. The reaction temperature rose slowly but did notexceed 30 C. After the addition of chlorothiophosphate, stirring at roomtemperature is continued for an additional two hours. The benzene layeris separated and the aqueous layer is extracted thrice with 20 ml.portions of benzene. The combined benzene fractions are dried overanhydrous magnesium sulfate, filtered and the benzene is evaporated. Theresidual solid is recrystallized from petroleum ether/ benzene to yield13.9 g. of colorless crystals, M.P. 8993 C. Yield: 83% of theory. Onfurther recrystallization, the melting point could be raised to 90-925C.

Analysis.-Calcd for C H N O PS C, 29.99; H, 5.45; N, 11.66; S, 26.69.Found: C, 29.54; H, 5.53; N, 111.61; S, 26.51.

The infrared spectrum (KBr pellet) showed a strong band at 1590 cm.-(C=N-- vibration), and strong bands at 1040 cmr 1020 cm. and at 780'cm.- (POC stretch).

EXAMPLE 8 2-(0,0-dimethylthiophosphorylimino)- 3-methylthiazolidine Asolution of 9.5 g. (0.082 moles) 2-imino-3-methylthiazolidine in ml.benzene is treated with 13.1 g. (0.082 equivalents) 25 (w./W.) sodiumhydroxide solution. To the resulting mixture are added slowly 13.1 g.(0.082 moles) O',O-dimethyl chlorothiophosphate in 30 ml. benzene. Thereaction temperature is held below 30 C. with the aid of a water bath.After drying the benzene layer and then evaporating the solvent, acolorless solid remained. Recrystallization from petroleum ether/benzenegave 15.8 g., M.P. 88-91" C. Yield: 80% of theory. The infrared spectrumof this material is identical to the spectrum obtained from theprocedure in Example 7, supra.

9 EXAMPLE 9 thiazolidine SCH: N

A mixture of 120.5 g. (0.500 moles)2(0,0-dimethylthiophosphorylimino)-3-methylthiazolidine, 400 ml. benzeneand 213 g. (1.50 moles) methyl iodide are refluxed for 80 minutes. Mostof the methyl iodide and benzene are evaporated. The remaining paleyellow liquid is redissolved in 500 ml. benzene and allowed to remain incontact overnight. A small amount of colorless solid by-productprecipitated during this period. The benzene solution is filtered andthe solvent evaporated. Some 113.5 g. of a viscous, colorless oilremained. Yield: 94% theory.

AntlZySiS.-C3.1Cd fOl' CH13N2O2PS2Z C, H, 5.45; N, 11.66; mol. wt.240.29. Found: C, 29.63; H, 5.76; N, 11.62; mole wt. (mass spectroscopy)240 (based upon S).

The infrared spectrum of this compound (liquid film) showed a strongband at 1590 cm.- (C=N vibration), a band at 1210 cm. (P=O), and bandsat 1040 cm.- and 780 cm. (P-O-C stretch).

EXAMPLE Preparation of the intermediateZ-[N-(chloro-O-ethylphosphorothiono)-imino] 3ethyl-5-methyl-l,3-oxazolidine 44.5 g. of phosphorothiodichloridate isdissolved in 300 ml. of anhydrous ethyl ether. To this mixture asolution of 64.0 g. 2-imino-3-ethyl-5-methyl-1,3-oxazolidine in 400 ml.anhydrous ethyl ether is added dropwise at -10 C. The reaction mixtureis stirred at room temperature for two hours. After filtering thesolvent is removed on a rotary evaporator. There is obtained 67.0 g.(yield: 95% of theory) n 1.5245.

Preparation of 2-[N-(O,S-diethyl phosphorodithio)-imino]-3-ethyl-5-methyl-1,3-oxazolidine A solution of 11.0 g.2-[N-(chloro-O-ethylphosphorothiono)-imino]-3-ethyl-5-methyl-1,3-oxazolidine in 50 m1. tetrahydrofuran was added to3.1 g. of ethanethiol and 2.0 g. of powdered sodium hydroxide in 100 ml.tetrahydrofuran at room temperature. The mixture is stirred for twohours at 50 C. The solution is dried with anhydrous MgSO filtered andthe solvent removed on a rotary evaporator. There is obtained ll.0 g.(yield: 92% of theory) of the title compound, n 1.5139.

EXAMPLE 11 Preparation of 2-N-[0-ethyl S(4-chlorophenyl)phosphorodithiono]-imino-3-ethyl 5methyl-1,3-oxazolidine A solution of 11.0 g. 2-[N-(chloro-O-ethylphosphorothiono)-imino]-3-ethyl-5-methyl-1,3-0xazo1idinein 50 ml.

of tetrahydrofuran is added to 7.2 g. p-chlorothiophenol and 2.0 g.powdered NaOH in 100 ml. tetrahydrofuran.

The mixture is stirred for two hours at 50 C. The reaction mixture isdissolved in ethyl ether and washed twice with 100ml. of 10% NaOHsolution and once with 100 ml. of water. The ether layer is then driedover anhydrous MgSO, and the solvent removed on rotary evaporator. Thereis obtained 14.7 g. (yield: 94% of theory) of the title compound n1.5753.

2 [N (chloro S methylphosphorothio)-imino]-3-ethyl-S-methyl-l,3-oxazolidine is prepared in the same manner asdescribed for 2- [N-(chloro-O-ethyl phosphoro- 10 thio)-imino]-3-ethyl 5methyl-1,3-oxazolidine starting with S-methyl thiophosphorodichloridate.

EXAMPLE 12 Preparation of 2- [N- (S-allyl,Smethyl phosphorodithio)-imino]-3-ethyl-5-mcthyl-1,3-oxazolidine A solution of 15.3 g.2-[N(chloro-S-methylphosphorothio)-imino]-3-ethyl-5-methyl-1,3-oxazolidinein 50 ml. tetrahydrofuran is added to 4.5 g. allyl thiol and 2.4 g.powdered sodium hydroxide in 100 ml. tetrahydrofuran. The mixture isstirred for two hours at 50 C. The mixture is dissolved in benzene andwashed once with 100 ml. saturated solution of NaHCO and twice with 100ml. water. The organic layer is dried over anhydrous MgSO and thesolvent removed on rotary evaporator. There is obtained 9.1 g. (yield:52% of theory) of the title compound, n 1.5607.

It is noted that when optically pure materials are used to preparecompounds within the scope of this invention, a variation ininsecticidal activity is observed. The preparation of such compounds,believed to be rich in one optical isomer due to retention ofconfiguration throughout the synthesis, is carried out by starting withan appropriate optically pure amino acid such as D- or L- alanine. Theamino acid is then acylated with an appropriate acylating agent such asacetic anhydride to yield an N-acyl amino acid which is then reducedwith lithium aluminum hydride to give a Z-subStituted-amino alkanol. Theamino alkanol is reacted with cyanogen bromide (BrCN) in the presence ofa base, such as powdered sodium hy droxide to yield the correspondingcyanamide. Treatment of the B-hydroxyalkyl cyanamide with a furtherquantity of sodium hydroxide promotes the ring-closure to thecorresponding imino oxazolidine. The imino oxazolidine is phosphorylatedwith the appropriate phosphorus containing acid chloride in a solution,such as benzene, in the presence of an acid acceptor such as sodiumhydroxide. When a thionophosphorus compound is prepared, rearrangementto the thiolophosphorus compound is accomplished by reaction with analkyl iodide in an appropriate solvent, such as benzene-hexane solution.

The above general procedure is illustrated by the following specificprepartions:

EXAMPLE 13 Preparation of the intermediate: N-acetyl-D-alanine D-alanine(25.0 g., 0.281 moles) is added to 100 ml. of water and then cooled inan ice bath while being rapidly stirred. Potassium hydroxide (18.5 g. ofKOH) in 50 ml. ofwater is added slowly, resulting in a clear solution.To this solution 28.6 g. of acetic anhydride is added with vigorousstirring, and the mixture stirred for 1 hour at room temperature. Theresulting clear solution is acidified with 23.4 ml. of concentratedhydrochloric acid, poured into an evaporating dish, and the solventallowed to evaporate. The concentrate is placed on a rotary evaporatorand further concentrated until a viscous semi-solid is obtained which isthen thoroughly titurated with ethyl acetate. The ethyl acetate isdecanted and dried over anhydrous sodium sulfate, filtered to removesolids, and stripped on a rotary evaporator to give a colorless oilwhich slowly crystallizes. A total of 35.4 g. (96%) of crude product isobtained which is used lowing specific preparations:

Preparation of the intermediate: N-ethyl-D-alaninol N-acetyl-D-alanine(35.4 g., 0.270 mole) is dissolved in 350 ml. of dry tetrahydrofuran and63 ml. of 4.2 M lithium aluminum shydride in ether added dropwise withrapid stirring at a rate such that the solvent refluxes gently. Afteraddition is complete, refluxing with rapid stirring .is continued for 3hours. After cooling the stirred mixture in an ice bath, 20 m1. of wateris added dropwise, followed by 20 ml. of 25% aqueous potassium hydroxidesolution, and 40 ml. of water. The precipitated solids are removed byfiltration, washed with tetrahydrofuran, percolated with hot ethanol,and again filtered. The combined filtrates are dried over anhydroussodium sulfate, and stripped of solvent. The oily residue is shaken withtetrahydrofuran and the supernatant liquid decanted, filtered, andstripped of solvent. There is obtained a yield of 15.8 g. (64%) of anamber oil.

Preparation of the intermediate: D" 2-imino-3-ethyl-4-methyl-1,3-oxazolidine N-ethyl-D-alaninol (17.6 g., 0.171 mole)prepared by the above-described method is dissolved in 75 ml. ofbenzene. Powdered sodium hydroxide (7.1 g.) is added and rapid stirringbegun. A solution of 18.1 g. of cyanogen bromide dissolved in 50 ml. ofbenzene is added dropwise to the above mixture which has been cooled inan ice bath. After the addition of cyanogen bromide is complete, another1 g. of powdered sodium hydroxide is added and the whole stirred for 2hours at room temperature. The solids are removed by filtration and thesolvent removed by a rotary evaporator. There is obtained a yield of19.0 g. (87%) of a wine-red oil which is vacuum flash distilled into aDry Ice trap using a hot water bath EXAMPLE 14 Prepartion of D2-[N-(0,0-dimethylphosphorothiono)-imino]-3-ethyl-4-methyl-1,3-oxazolidineThe above oxazolidine (11.5 g., 0.0898 mole) is dissolved in 100 ml. ofbenzene and 3.7 g. of powdered sodium hydroxide added. 0,0-dimethylphosphorothionochloridate (14.5 g., 0.898 mole) is dissolved in 25 ml.of benzene and is added to the above rapidly stirred mixture. Thetemperature is kept below 45 by use of a water bath. After stirring for/2 hour at room temperature another 1 g. of powdered sodium hydroxide isadded and the whole stirred for another 2 hours at room temperature. Atthe end of this time, water is added to the reaction mixture, thebenzene layer separated and the aqueous phase is washed with benzene.The combined organic layers are washed with water, saturated sodiumchloride solution, and dried over anhydrous sodium sulfate. The solventis removed by evaporation to yield 15.4 g. (68%) of an amber oil whichcrystallizes on standing overnight.

EXAMPLE 15 Preparation of 2-[N-(O,S-dimethylphosphorothiolo)- imino]-3-ethyl-4methyl-1,3-oxazolidine The thiono compound (8 g.) prepared bythe above procedure in Example 13 is dissolved in 50 ml. of benzene, ml.of methyl iodide added, and the solution refluxed for 1 hour. Thesolution is cooled and the solvent removed on a rotary evaporator toyield an amber oil, 21 1.5265.

GENERAL PROCEDURE In general, the synthesis of compounds of the type fRt lower alkoxy fi N 1 3. lower alkoxy O L R0 R1 and 1' m lower alkoxy-N Y- :1 lower alkoxy O 4 R begins by reacting a geometrically pure cisor trans isomer of a symmetrical epoxide with an appropriate primaryamine to give either a threo or erythro-p-aminoalcohol.

EXAMPLE l6 Erythro-l methyl 2-ethylamino propanol To 64.3 g. of astirred 70% aqueous solution of ethylamine is added dropwise 36.0 g. oftran's-Z-butene oxide. The solution is allowed to stir overnight at roomtemperature, then at 34-45" for approximately 7 hours, then againovernight at room temperature.

The resulting solution is then placed briefly on a rotary evaporator at35 to remove unreacted ethylamine and epoxide. Ether (300 ml.) is thenadded and the two phase system rapidly stirred with anhydrous sodiumsulfate. The ether layer is decanted and dried over anhydrous magnesiumsulfate. The ether is removed on a rotary evaporator leaving 14.1 g. ofa colorless liquid.

2-imino-3-ethyl-cis-4,5-dimethyl-1,3-oxazolidine To 13.6 g. of the aboveamino alcohol in 75 ml. of benzene is added 4.8 g. of powdered sodiumhydroxide. The mixture is cooled in an ice bath and stirred rapidlyduring the dropwise addition of 12.3 g. of cyanogen bro mide in 50 ml.of benzene. After the addition of 12.3 g. of cyanogen bromide iscomplete another 1.0 g. of powdered sodium hydroxide is added and themixture stirred for 2 hours at room temperature. The mixture is filteredto remove solids and the solvent removed on a rotary evaporator to give15.2 g. of a slightly brown mobile liquid.

2- [N- 0,0-dimethylphosphorothiono -imino] -3 -ethylcis-4,5-dimethyl-1,3-oxazolidine To 14.8 g. of the above oxazolidine in75 ml. benzene is added 4.2 g. of powdered sodium hydroxide. The mixtureis stirred rapidly and a solution of 16.8 g. of 0,0-dimethylphosphorothionochloridate in 25 ml. of benzene is added dropwisesuch that the temperature did not exceed 45 After addition of thechloridate is complete, another 0.5 g. of powdered sodium hydroxide isadded and the mixture stirred for a total of 2% hours. The solids areremoved by filtration and the solution dried over anhydrous magnesiumsulfate. The solvent is removed on a rotary evaporator to give 26.1 g.of the title compound alight amber oil.

GENERAL PROCEDURE The compounds of the formula compounds with methyliodide in benzene. The following example is illustrative of this generalmethod.

13 EXAMPLE 1'! 2- [N- O,S-dimethylphosphorothiolo -imino]-3-ethylcis-4,5-dimethyl-1,3-xazolidine 2[N-(0,0-dimethylphosphorothiono -3 -ethyl-cis-4,5-

of water. The mixture is stirred a few minutes, filtered, and thefilter-cake extracted with ether. The ether solution is dried overmagnesium sulfate and stripped in vacuo, and the residue is distilled.There is obtained a yield of 43.5 g. (74.4%), B.P. 61.563/2.6 mm.theory. The

dimethyl-1,3-oxazolidine is dissolved in 5 spectrum confirmed thestructure of benzene, ml. of methyl iodide added and the whole The aboveamino 1 1 35 1 g 03 mole) d 'e f 1 At the end of this tlme the 50111-dered sodium hydroxide (12.0 g., 0.3 mole) are placed tron ls filteredto remove a small amount of solid and the in 200 1 of dry benzene Asolution of cyanogen solvent removed on a rotary evaporator to glve thetitle 10 mide (30.9 g., 0.3 mole) in 100 ml. of dry benzene is compounda reddlsh amber added with stirring at 5-15". The mixture is thenstirred EXAMPLE 18 one hour at ice-bath temperature and two hours atroom temperature. The mixture is filtered, the filtrate treatedPreparation of 2-1m1no-3 lso-propylperhydro-1,3-oxaz1ne with Mgsob andrefiltered, and the Solvent is removed Preparation of the intermediate:Ethyl B isopropylvaeue- The fesldhe Showed a Strong amino propionate .Toisopropylamine g band at GEL-1 111 lnfrared. ThlS product 15 man].-mole) in 300 ml. of ethanol is added ethyl acrylate (110 y the uheyehledy h v g., 1.1 mole) at 4o-so with stirring. The mixture is kept of theuncychzed cyanamlde 1s d1sso1ved m at steam bath temperature for onehour. The solvent is 400 0f h i 8- 0f Powdered eallstlefldded a removedthrough a Vigreux column in vacuo and the the mlxture stlrred for fivehours. Some heat is evolved. residue is distiugd. There is obtained ayield of 1542 Removal of the solvent left an oil. This is distilledtwice 91% of theory of the intermediate B.P. 68.5-70/6.4 mm. i e secondtune through a vlgreux u The IR spectrum showed the expected bands. Theproduct is collected at 48-50/.35 mm. No CEN Preparation of theintermediate: Isopropylamino-S-proe was Pbsel'ved m the lhfl'al'edSpectrum There e panol.-To 120 ml. of a 4.2 molar solution of lithiumtamed Yleld of 17 (433% based on the cyanamlde): aluminum hydride (19g., .5 mole) in ether is added 100 of the htle p y r eml. additional dryether. A solution of ethyl-fl-isopropyl- The other perhydm'lfi'oxazmes qs herem are aminopropionate (95.4 g., .6 mole) in 50 ml. of dry ether Pe e analogeus manner stal'hhg Wf the p is added dropwise at 15-2' 5. Themixture is stirred for P matemKIS asfmtlmed heremabove I one-half hourat room temperature and refluxed for one The follo'wlhg 15 f table of -Pfepl'esehtahve hour. Nineteen milliliters of water are slowly added tothe of those emhodled 1h h Present lhvehhoh- Compound mixture withstirring and cooling, followed by 19' ml. of numbers have been asslghedto them and are used for 15% sodium hydroxide solution and an additional57 ml. identification throughout the balance of the specification.

TABLE I Bl\Il /P-N-CN-R| R: Y-

R4 R1 liwherein Q, is -('L(%- R5 R5 Com ound no or melting num er Y R1R: R: Rt R1 R5 R1 point, C. 0 OHIO CHIS 02H; cm H H H Yellow 011. 0 CzHrCHsS CzH cm H H H Do. 0 ceHro CHsS 02H OH; H H H Do. O CH:() CHsS C1H| HH H H D0. 0 CH0 CHQO 0211; H H H H 54-57. 0 C1130 C1130 02H: 02H H H H1.5175. 0 CH0 CHlS 02H; 02H; H H H Red brown 011. O 03H CHIS CH|OC1H|CH1 H H H Dark Rd 011. 0 01H CzHnO CHaOCzHt OH! H H H 1.5078. 0 oHiocHis CHzCH=CHr OH: H H H Yellow 011 0 CH0 CHIO l-CtHt OH: H H H 5109. 0CHsO CH S 1"C4H9 OH: H H H Yellow 011 o CHrO CHsS CHSOCQH OH; H H H Do.0 03H: CzHsO 1-C4Hg CH1 H H H D0. 0 CHO CH1O Phenyl H H H H Semi-solid.0 CHiO oHis t-clHt H H H H Do. 0 01110 CHrS l-CtH-t H H H H Viscous 011.0 CHrO CHIO n-CcHa H H H H D0. 0 CHsO CHis n-ctm H H H H Do. 0 CHIO CHaOt-otHt H H H H 1075-109. 0 CH0 cHrs 1-CIH1 OH; H H H Regdlsh brown 0CHSO crno 01m 0H. 011. H H 1.512 1. 0 cHio CHIS crHi CH; OH; H H Yellow(crude). O CaHs CaHsO CzHs CH1 OH: H H 1.5022. 0 01H; CHrS 02H. 0H. OH,H H Yellowdtail l1 9 r 0 CHrO CHzO l-orHr CH1 H H H 1.51 55. 0 OHIO eC1121: C2115 CHI H H H 1.5150. 0 011,0 n-CsHrS 01H; OH; H H H 1.5011. 0CHaO l-CsH1S ClHs CH: H H H 1.5038. 0 cHio II-CHQS 02H, OH; H H H1.5027. 0 C|H|O C1H3S 02H; OH; H H H 1.5139. 0 CeHrO pOl-phenyl-B 02HGHr H H H 1.5753. 0 CzHsO CHsS 02H: OH: H H H 1.5386. 0 031150p-NOgphenyl-O CQH; CH; H H H 1.5358. 0 CzHgO ll-CaH1S 02H; CH3 H H H1.5280. 0 CIHIO CaHsO I C2H| H CH; H H 0 01H CzHs. OH: H H H H 1.5563. 0CHlO CHIS CzH; CH: H H H 1.5597. 0 CHrO pOl-phenyl-S CzHs OH: H H H1.6163. 0 011m 2 r 01H; OH; H H H 1.5490. 0 oHto -Noa lien l-o CzHs OH:H H H 1.5633. 0 CH0 n-CaH-yS OtHr OH; H H H 1.5524. 0 cHro 01H; OH. H HH 1.5390.

up" or melting R1 point, 0.

TABLE I-Continued Compound number i-CrH1 1.5178 (L). i-C4Hg 69.5-71.5 (Ll-C4H. CH:

HHHHHHHHHHHHHH HHHHHHHHHHHHHH mmmm CCCCC HHHHHHHH H 1.5607. 1 .5907.Reddish brown HH HHHHHHHHHHHHHH CHI C2115 CH2=CHCHP CHa=CHCHr- PhenylCH:

H 0 E H o 0 CH0; w H E o CHiO mmmH 00cc p-NOzphenyl-O D-NOIDhGIlYl-OHIO2,4,6-ClzDhenyl-O p-CHgS-phenyl-O p-ON-phenyl-O p-C (CH1) :phenyl-O2,4-Clzphenyl-O -Cl-phenyl-O Liquid. Semi-solid. Liquid. Do. Do.

HHHHHHHHHHHHHHHHHH HHHHHHH HHHHHHH e v .w a w m a S CHzGHzCHI CHnCHzCHICal-I11 sHn CHzCH CHzCH CHtO OHIO

89....---.-.. O S CHQO 97........-....- B S CHaO HHHHHHHHHH HHHHHHHHHHHHHHHHHHHH HHHHHHHHHH CHzCH=C ClCH OHzCH=CC1CHa CHtCHaO OHlCHzO SSSSSSSOSOSOSOSOO Low melti solid. Do. Viscous oil. Yellow oil. Viscous oil.99-102.

1B wherein Q is CH1CHzCH:-

C H|0 CzH CH,0H=0H, i-CIH Systemic evaluation test.This test evalatesthe sysplants are placed in bottles containing 200 m1. of the test temictoxicity by root absorption and upward translocation solution and heldin place with cotton plugs. Only the roots of the candidate systemiccompound. The two-spotted mite, are immersed. The solutions are preparedby dissolving the compounds to be tested in a suitable solvent, usuallyacetone, and then diluting with distilled water. The final acetoneconcentration never exceeds about 1%. Immedias host plants for thetwo-spotted mite. The pinto bean ately after the plants are placed inthe test solution, they 108..--...-.-... S O CH|O Tetranychus urticae(Koch) and the bean aphid, Aphis fabae (Scop.), are employed in testsfor systemic activity. Young pinto bean plants in the primary leaf stageare used are infested with the test species. Mortalities are determinedafter seven days. The percentage kill is determined by comparison withcontrol plants which are placed in distilled water only. The LD- valueis calculated using well-known procedures. LD- values for thetwo-spotttd mite are found in Table II under column 2SM- SYS; and forbean aphid under column BAS.

Young nasturtium plants (Tropaeolum sp.) are used as the host plants forthe bean aphid. The host plants are transplanted intoone pound of soilthat has been treated with the candidate compound. Immediately afterplanting in the treated soil the plants are infested with the aphids.Concentrations of toxicants in the soil ranged from p.p.m. per pound ofsoil downward until an LD- value is obtained. Mortality is recordedafter 72 hours. Comparison is made with control plants placed inuntreated soil.

Insecticidal evaluation tests.--'Ihe following insect species aresubjected to evaluation tests for insecticidal activity.

( l) Housefly (HF)Musca dom estica (Linn.) (2) Lygus bug (LB )--Lygushesperus (Knight) Aliquots of the toxicants, dissolved in an appropriatesolvent, are diluted in water containing 0.002% of a wetting agent,Sponto 221 (a polyoxyether of alkylated phenols blended with organicsulfonates). Test concentrations range from 0.05% downward to that atwhich 50% mortality is obtained. In the tests, for these species, 10one-month old nymphs of the lygus bug are placed in a circular cardboardcage sealed on one end with cellophane and covered by a cloth netting onthe other. Test concentrations for the lygus bug ranged from 0.05%downward to that at which 50% mortality was obtained. Each of theaqueous suspensions of the candidate compounds are sprayed onto theinsects through the cloth netting by means of a hand spray gun. Percentmortality in each case is recorded after 72 hours, and the LD- valuesexpressed as percent of toxicant in the aqueous spray are recorded. Theresults are in Table II under column LB.

The following procedure is used to test housefiies. A stock solutioncontaining 0.1 percent by weight of the toxicant in an appropriatesolvent is prepared. Aliquots of this solution are combined with 1milliliter of an acetonepeanut oil solution in a glass Petri dish andallowed to dry. The aliquots are selected to achieve desired toxicantconcentration ranging from 100 mg. per Petri dish to that at which 50%mortality was attained. The Petri dishes are placed in a circularcardboard cage, closed on the bottom with cellophane and covered on topwith cloth netting. Twenty-five female houseflies are introduced intothe cage and the percent mortality is recorded after 48 hours.

The LD- values are expressed in terms of percent concentration or ,ug.per 25 female flies. LD- values obtained in the above-mentioned houseflytest are found in Table II under column HF.

Systemic test.-Salt-marsh caterpillar-Estigmene acrea (Drury): Aliquotsof the toxicant dissolved in appropriate solvents are diluted in waterand placed in glass bottles. Concentrations of active ingredient rangefrom 10 ppm. to that at which 50% mortality is obtained. Kidney beans(Phaseolus vulgaris), supported by cotton plugs, are inserted into thesolution so that the roots and major portion of the stem are completelyimmersed. Salt-marsh caterpillar egg masses (10 to 30 eggs) on smallpieces of tissue paper are pinned to the kidney bean leaves and allowedto hatch. Mortality is recorded after five days and the LD- values areexpressed as parts per million (p.p.m.) of toxicant in the aqueoussolution. The values are found in Table II under the column SMC-Sys.

The compounds are also active against two-spotted mite (2-SM)(Tetranychus urticae (Koch.) Lima bean plants (Phaseolus sp.) areutilized as the host plant and infested with 50 to mites of variousages. Twenty-four hours after infestation they are sprayed to the pointof run off with aqueous suspension of the toxicant. Test concentrationsrange from 0.05% to that at which 50% mortality is obtained. The valuesobtained in this test are found in Table 11 under the columns ZSM- PEand ZSM-Eggs.

The compounds are also active against bean aphid (Aphis fabae (Scop.))as a contact toxicant. The same test procedure as given for thetwo-spotted mite above is used for the bean aphids except nasturtium(Tropaeolum sp.) plants approximately 2 to 3 inches tall are used as thehost plant. The LD- values obtained for the compounds of this inventionare found in Table II undercolumn BA.

As previously mentioned, the herein described compounds produced in theabove described manner are phytotoxic compounds which are useful andvaluable in controlling various plant species. Compounds of thisinvention are tested as herbicides in the following manner.

Pris-emergence herbicide test.0n are day preceding treatment, seeds ofseven ditferent weed species are planted in individual rows using onespecies per row across the width of the flat. The seeds used are hairycrabgrass (Digitaria sanguinatis (L.) Scop.), yellow foxtail (Setariaglauca (L.) Beauv.), watergrass (Echinochloa crusgalli (L.) Beauv.),wild oats (Avena fatua (L.)), redroot pigweed (Amaranthus retroflexus(L.)), Indian mustard (Brassica juncea (L.) Coss.) and curly dock (Rumexcrispus (L.)). Ample seeds are planted to give about 20 to 50 seedlingsper row, after emergence, depending on the size of the plants. The flatsare watered after planting. The spraying solution is prepared bydissolving 50 mg. of the test compound in 3 ml. of a solvent such asacetone containing 1% Tween 20' (polyoxyethylene sorbitan monolaurate)and diluting with a small amount of water. The following day each flatis sprayed at the rate of 20 pounds of the candidate compound pergallons of solution per acre. An atomizer is used to spray the solutionon the soil surface. The flats are placed in a greenhouse at 80 F. andwatered regularly. Two weeks later the degree of weed control isdetermined by comparing the amount of germination and growth of eachweed in the treated flats with weeds in several untreated control flats.The rating system is as follows:

TABLE IL-INSECTICIDAL EVALUATION RESULTS LD-i values 2-SM SMC, CompoundHF LB B BAS SYS Eggs SYS number (pg/25 (percent) (percent) (p.p.m.)(p.p.m.) (percent) (percent) (p.p.m.)

21 An activity index is used to represent the total activity on allseven weed species. It is the sum of the number of plus marks, so thatan activity index of 21 represents complete control of all seven weeds.

Post-emergence herbicide test.--Seeds of five weed species includinghairy crabgrass, watergrass, wild oats, Indian mustard, and curly dockand one crop pinto beans (Phaseolus vulgaris), are planted in flats asdescribed above for pre-emergence screening. The flats are placed in thegreenhouse at 7285 F. and watered daily with a sprinkler. About 10 to 14days after planting when the primary leaves of the bean plant are almostfully expanded and the first trifoliate leaves are just starting toform, the plants are sprayed. The spray is prepared by weighing out 50mg. of the test compound, dissolving it in ml. of acetone containing 1%Tween 20 (polyoxyethylene sorbitan monolaurate) and then adding 5 ml. ofwater. The solution is sprayed on the foliage using an atomizer. Thespray concentration is 0.5% and the rate would be approximately 20lbs/acre if all of the spray were retained on the plant and the soil,but some spray is lost so it is estimated that the application rate isapproximately 12.5 lbs/acre.

Beans are used to detect defoliants and plant growth regulators. Thebeans are trimmed to two or three plants per fiat by cutting off theexcess weaker plants several days before treatment. The treated plantsare placed back in the greenhouse and care is taken to avoid sprinklingthe treated foliage with water for three days after treatment. Water isapplied to the soil by means of a slow stream from a watering hosetaking care not to wet the foliage.

Injury rates are recorded 14 days after treatment. The rating system isthe same as described above for the preemergence test where and are usedfor the difierent rates of injury and control. The injury symptoms arealso recorded. The maximum activity index for complete control of allthe species in the post-emergence screening test is 18 which representsthe sum of the plus marks obtained with the six plant species used inthe test.

The concentration of a compound of the present invention constituting anefiective amount and the best mode of administration to an insect oracarid pest or its habitat may be easily determined by those skilled inthe art of pest control, as exemplified by the procedures describedhereinabove. As shown above, the compounds of the present invention arealso useful as pre-emergence or post-emergence herbicides, and can beapplied in a variety of ways at various concentrations. In practice thecompounds are formulated with an inert carrirer utilizing methodswell-known to those skilled in the art, thereby making them suitable forapplication as dusts, sprays, drenches and the like. The amount applieddepends upon the nature of the seeds or plants to be controlled and therate of application may vary from one to lbs. per acre. One particularlyadvantageous way of applying the compound is as a narrow band along therow crop, straddling the row.

Various changes and modifications can be made with out departing fromthe spirit and scope of the invention described herein as will beapparent to those skilled in the art to which it pertains. It isaccordingly intended that the present invention shall only be limited bythe scope of the claims.

What is claimed is:

1. A compound according to the formula Y CH wherein X and Y are oxygenand sulfur, R is lower alkoxy, R is lower alkoxy or lower alkylthio; Ris lower alkyl or alkenyl.

2. A compound according to claim 1 in which X is sulfur, Y is oxygen, Ris methoxy, R is methoxy and R is ethyl.

3. A compound according to claim 1 in which X is sulfur, Y is oxygen, Ris methoxy, R is methoxy and R is allyl.

No references cited.

HENRY R. JILES, Primary Examiner M. A. M. CROWDER, Assistant ExaminerU.'S. Cl. X.R. 260-244 R

